Comparative evaluation of size-exclusion chromatography and viscometry for the characterisation of cellulose.

The analysis using size-exclusion chromatography (SEC) with multi-angle light scattering (MALS) and differential refractive index (DRI) detection of cellulose dissolved in lithium chloride/N,N-dimethylacetamide (LiCI/DMAc) is evaluated and compared to two other methods currently used for cellulose analysis. These are SEC with low-angle light scattering (LALS) and ultra-violet detection of cellulose derivatised to tricarbanilates (CTC), and viscometry in cadmium triethylene diamine dihydroxide (cadoxen). The cellulose source is Whatman No. 1 paper, unaged or artificially aged with a combination of heat and humidity. The values of the molar mass (Mr) averages of cellulose obtained with the different methods resulted quite different for both aged and unaged paper. SEC of cellulose in LiCl/DMAc provided the highest Mr averages values, followed by SEC of CTC, while viscometry yielded the lowest values. These differences were more or less pronounced depending on the initial degradation state of the paper. Several hypotheses are presented in order to explain these discrepancies and each method is discussed on the basis of its suitability to characterise the aging-induced degradation.

[1]  M. H. Irfan,et al.  Chemistry of polymers , 1998 .

[2]  Charles L. McCormick,et al.  Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide , 1985 .

[3]  M. Agrawal,et al.  MIXED LIGAND COMPLEXES OF ALKALINE EARTH METALS: PART-X. Mg(II), Ca(II), Sr(II) and Ba(II) COMPLEXES WITH 5-BROMOSALICYLALDEHYDE AND b-DIKETONES , 2003 .

[4]  S. Fischer,et al.  7Li NMR as probe for solvent–cellulose interactions in cellulose dissolution , 2001 .

[5]  A. Turbak.  Recent developments in cellulose solvent systems , 1984 .

[6]  S. Moe,et al.  Characterization of cellulose by SEC-MALLS , 2002 .

[7]  A. Dupont.  Cellulose in lithium chloride/N,N-dimethylacetamide, optimisation of a dissolution method using paper substrates and stability of the solutions , 2003 .

[8]  D. Fengel,et al.  Changes in cellulose structure during dissolution in LiCl:N,N-dimethylacetamide and in the alkaline iron tartrate system EWNN , 1996 .

[9]  Tetsu Uesaka,et al.  Prediction of paper permanence by accelerated aging I. Kinetic analysis of the aging process , 1996 .

[10]  André M. Striegel,et al.  ADVANCES IN THE UNDERSTANDING OF THE DISSOLUTION MECHANISM OF CELLULOSE IN DMAc/LiCl , 2003 .

[11]  H. Sixta,et al.  Hydrolytic processes and condensation reactions in the cellulose solvent system N,N-dimethylacetamide/lithium chloride. Part 2: degradation of cellulose , 2003 .

[12]  A. Striegel,et al.  Molecular characterization of polysaccharides dissolved in Me2NAc-LiCl by gel-permeation chromatography , 1995 .

[13]  A. Striegel.  Theory and applications of DMAC/LICL in the analysis of polysaccharides , 1997 .

[14]  P. Flory.  Principles of polymer chemistry , 1953 .

[15]  M. Terbojevich,et al.  Mesophase formation and chain rigidity in cellulose and derivatives. 3. Aggregation of cellulose in N,N-dimethylacetamide-lithium chloride , 1985 .

[16]  A. El-Kafrawy.  Investigation of the cellulose/LiCl/dimethylacetamide and cellulose/LiCl/N‐methyl‐2‐pyrrolidinone solutions by 13C NMR spectroscopy , 1982 .

[17]  H. Sixta,et al.  Degradation of cellulosic materials by heating in DMAc/LiCl , 2002 .

[18]  B. L. Browning,et al.  Methods of wood chemistry , 1967 .

[19]  Robert Evans,et al.  Molecular weight distribution of cellulose as its tricarbanilate by high performance size exclusion chromatography , 1989 .

[20]  C. McCormick,et al.  THE LITHIUM CHLORIDE/DIMETHYLACETAMIDE SOLVENT FOR CELLULOSE: A LITERATURE REVIEW , 1990 .

[21]  M. Lindström,et al.  Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp , 2003 .

[22]  F. Pla,et al.  Molecular Weight Distribution of Cellulose by On-Line Size Exclusion Chromatography — Low Angle Laser Light Scattering Part I: Basic Experiments and Treatment of Data , 1987 .

[23]  H. Blair,et al.  Spectroscopic investigation of cellulose degraded celluloses, and their phenylhydrazine derivatives in relation to assessment of degradation , 1972 .

[24]  M. Strlič,et al.  Enthalpic interactions in size exclusion chromatography of pullulan and cellulose in LiCL-N,N-dimethylacetamide. , 2002, Journal of chromatography. A.

[25]  T. Röder,et al.  The effect of water on cellulose solutions in DMAc/LiCl , 2002 .

[26]  Arnis Treimanis,et al.  Problems of the MMD analysis of cellulose by SEC using DMA/LiCl: A review , 2002 .

[27]  T. Röder,et al.  Solutions of cellulose in N,N-dimethylacetamide/lithium chloride studied by light scattering methods , 2001 .

[28]  Matija Strlič,et al.  Evaluation of size-exclusion chromatography and viscometry for the determination of molecular masses of oxidised cellulose , 1998 .

[29]  F. Sundholm,et al.  Preparation of cellulose samples for size-exclusion chromatography analyses in studies of paper degradation. , 2003, Journal of chromatography. A.

[30]  L. L. Lloyd,et al.  Molecular weight characterization of underivatized cellulose by GPC using lithium chloride-dimethylacetamide solvent system , 1990 .

[31]  S. Moe,et al.  SIZE EXCLUSION CHROMATOGRAPHY OF CELLULOSE DISSOLVED IN LiCl/DMAC USING MACROPOROUS MONODISPERSE POLY(STYRENE-CO-DIVINYLBENZENE) PARTICLES , 2000 .

[32]  W. Brown,et al.  Aggregation of cellulose in lithium chloride/N,N-dimethylacetamide , 2000 .

[33]  T. Heinze,et al.  Determination of empirical polarity parameters of the cellulose solvent N,N‐dimethylacetamide/LiCl by means of the solvatochromic technique , 1998 .

[34]  A. Potthast,et al.  The investigation of the influence of water and temperature on the LiCl/DMAc/cellulose system , 2003 .

[35]  P. Wyatt.  Light scattering and the absolute characterization of macromolecules , 1993 .

[36]  E. Kamińska.  Determination of Degree of Polymerization of Cellulose in Ligneous Papers , 1996 .

[37]  T. Röder,et al.  The cellulose solvent system N,N-dimethylacetamide/lithium chloride revisited: the effect of water on physicochemical properties and chemical stability , 2002 .

[38]  Tetsu Uesaka,et al.  ACCELERATED AGING OF PAPERS OF PURE CELLULOSE - MECHANISM OF CELLULOSE DEGRADATION AND PAPER EMBRITTLEMENT , 1994 .

[39]  R. Evans,et al.  Pyridine-catalyzed depolymerization of cellulose during carbanilation with phenylisocyanate in dimethylsulfoxide , 1991 .